Polymeric sulphonamide



Patented June 15 1943 POLYMERIC SULPHONAMIDE Gerard J. Berchet, Wilmington, Del assignor to .E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application October 4, 1939, Serial No. 297,963

14 Claims. (cl. 260-556) This invention relates to polymeric materials, and more particularly to polymeric sulphonamides.

' This invention hasas an object the production of new linear polymers. A further object is the manufacture of new compounds and compositions of matter comprising polymeric sulphonamides.

My-new polymeric sulphonamides may be obtained by reacting an aliphatic disulphonyl halide with a diamine, which may be either aliphatic or aromatic. As used herein, the term, aliphatic, will include cycloaliphatic.

The disulphonyl halide has the formula HaLSOz-R-SOcHal where R is a divalent aliphatic radical containing a chain of at least three atoms,

and the diamine has the formula R'HN-R"-NRH where R is hydrogen or a monovalent hydrocarbon radical and R" is a divalent organic radical containing a chain of at least two atoms, both R and B" being free of substituents'reactive with the functional groups, that is, with the sulphonyl or amino groups. In the preferred embodimentof the invention R is a polymethylene chain, R

is hydrogen and R" is an aliphatic, polymeth-.

ylenic radical.

The new polymeric sulphonamides are characterized by recurring structural units of the I formula groups. The diamine may be either aliphatic or aromatic, and the reaction is carried out in a solvent or diluent at temperatures of to 200 (3., a hydrogen halide acceptor such as sodium hydroxide or excess diamine being present to remove the hydrogen chloride as formed. The reaction usually is vigorous and ordinarily'becomes complete in one to two hours. When a primary amine is used, the polysulphonamide conveniently can be isolated as the alkali salt, which is insoluble in manyorganic solvents. By subsequent acidification, the salt is converted to the free sulphoide.

A typical method of preparation is as follows:

One equivalent of the disulphonyl chloride in dioxan solution is added during twenty to thirty minutes to a well-agitated dioxan solution con-- taining two equivalents of the diamine at a temperature of 0 C. Potassium hydroxide, equivalent to the disulphonyl chloride reacted, is added as a five per cent aqueous solution to remove the hydrogen chloride formed in the sulphonation reaction. A second equivalent of the disulphonyl chloride in dioxan is then introduced during an interval of twenty to thirty minutes,

followed by addition of sumcient aqueous potassium hydroxide to precipitate the insoluble potassium salt of the polysulphonamide. The polysulphonamide is then obtained upon acidification of this potassium salt.

An alternative procedure is to add two equivalents of diamine to a well-stirred dioxan solution containing one equivalent of disulphonyl halide at a temperature of to 50 C. After one hour, the solvent is removed in a vacuum, and the diamine dihydrohalide is separated from the polysulphonamide by extraction with water.

An essential condition for the success of any of these procedures is that neither reactant contain free acidic groups such as carboxyl or sulphonic acid groups.

' The following examples, in which the parts are by weight unless otherwise indicated, are further illustrative of methods for practicing the invention. The first three examples show the One half of a solution of para-cyclohexanedisulphonyl chloride (11.26 parts) in 250 parts of purified dioxan is added to a solution of hexamethylenediamine (4.86 parts) dissolved in 3 parts of dioxan at C. Pcstasslum hydroxide (6.68 parts) is added as a 10 percent aqueous solution followed by the addition of the other hall of the disulphonyl chloride at 10 C. A secend portion of potassium hydroxide (6.68 parts) as a 10% aqueous solution is added and the white insoluble polymeric potassium salt is removed by filtration. Upon acidification of the potassium salt, a white powder is obtained which melts at This polysulionamide is soluble in hot phenol or ethylene glycol and can he dissolved in cold formic acid. It is insoluble in most of the other organic solvents, such as alcohol, ether, benzene, chlorolorm, etc.

Eszample Ir In a vessel provided with s. stirrer and two graduated seperotory funnels is placed 250 parts of a. purified dioxsn solution containing hexamethylenedismine (4.86 parts). One graduated seporatory funnel contains 50 ports of a cliomn solution of pers-cyclohexonedisulphonyl chloride (11.76 parts) while the other funnel contains 50 ports of an aqueous solution of potassium hydroxide (6.68 ports). To the vigorously stirred and cooled amine solution C.) ere added simultaneously the disulphonyl chloride and potessium hydroxide solutions. Ey noting the amount of eech reagent added through the ered= ueted seporetory funnels, it is possible to momte'in a slight excess of disulphonyl chloride in the reaction The totsl addition of the reagents tolres so minutes euol then on additional equivalent (6.68 ports) oi potessium hyurorlole is i To 300 parts of an ether solution containing hexamethylene-diamine (9.72 parts, 2 moles) is added the calculated quantity oi paracyclohexanedisulphonyl chloride (11.76 parts, 1 mole). A white precipitate is formed at once with con-' siderable evolution of heat. After extraction of the precipitate three times with boiling water, to remove the uiamine dihydrochloride. there remains a. white solid melting at 180 C. By

'titrating the end groups of this poly-sulphonamide with acid and alkali, the molecular weight of the polymer is shown to be 1,300.

Example IV Poly- [hexamethylene propanedisulphonamidel.

1,3-propanedisulphonyl chloride 16.20 parts) is dissolved in ports of purified dioxsn and half or the solution is added to hexamethylene gllamine (7.81 parts in- 90 parts of dioxan) at 75 C. The slurry lscooled to 10 C. and 7.54 parts of potassium hydroxide as a 10 per cent aqueous solution is added, followed by the balonce 0! the disulphonyl chloride solution. The potassium salt of polysulphonsmide precipitates upon further addition of potassium hydroxide give intsrpolymers.

(7.54 parts of a, 10 per cent aqueous solution).

The potassium salt (5.5 parts) is filtered and washed thoroughly with water, in which it is not appreciably soluble.

The polymeric P tassium salt is titrated with Just suflicient acid to liberate the 'free P01?- sulphonsmide. This polymeric product is th n shown to contain basic (smino) .and acidic (sulphonic acid) end nouns by titration with acid 5nd alkali respectively. These tltrntions demonstrste that the polymer has an sversze moloculsrwolzht of 1,380. The tree polysulphonnmlde is 0. white powder meltins' at 200 C.

The polymeric sulphonemides described herein may also be described in terms or their hydro products. The hydrolysis usually is accomplished by heating a concentrated aqueous hydrochloric acid or hydrobromic acid solution containing the polysulphonamide for three to six hours at peratures of to 2% C. under a, pressure of 'IOO to 800 lb. gouge. Under these conditions, the polysulphonemicles are hydrolyzed to the tile dlhyclrohullde, u. hydrocarbon and sulphur trioxicle, according to the following typical couch tion:

E H n no: --(CHz)0NSOz(CH:)sSOsN- 1 5-6-1;

- ucnmmouommeol cs0, one

Illustrations of aliphatic olisulphonyl halides which may replace those mentioned in the loregoing examples are: decene Llu-lphonyl chloride, hermne-LB-chsulphonyl chloride, pentene-lfi-dlsulphonyl chloride, 2,5-dimethyl herione-lfi-disulphouyl chloride, 2-tertiery butylhexsne-lfi-disulphonyl chloride, fi-ethorrybutsne-Le-disulphonyl chloride, end 3-hexene-1,(i- (ilsulphonyl chloride. Aliphatic disulphonyl holides containing hetero atoms also can be our-- played, as for example, 3-o2ra-pentane-l.,5-cllsulphonyl chloride (010280 1, .c *CHzBOaCl). S-thia-pentane- 1,5-disulphonyl chloride, and 3,6- dioxa-octane-l,S-disulphonyl chloride.

In place or the chlorides, the aliphatic sulphonyl fluorides or aliphatic sulphonyl bromides also can be employed. Sulphonyl iodides, however, due to their instability and diillculty of preparation, are less suited for the synthesis of polysulphonamicles.

Diamines which can be used in synthesizing polysulphonamldes, and in which both amino groups are hydrogen-bearing and are the sole amide-forming groups, include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,6-diamino-3-hexene decamethylenediamine, psraphenylenediamine, metaphenylenediamine, benzidine, 1,5-diamine-3-oxapentane (HsNCHaCHzOCI-BCHzNI-Ia), 1,8-dlamine-3,6-dioxa-oct'ane HaNCHzCHsOCHsCHaOCHsCHsNHs) beta, bets-diaminodiethyl sulphide, bets-methyl hexamethylenedismlne, and ortho-nitro-psrsphenylenedismine. In addition to these dlprlmsry dismines, their N, N'-dislkylsted or .dl- 1 arylsted derivatives also can be employed. Thus. the N,N'-dimethyl or N,N'-diphenyl derivatives or the above mentioned diprlmary diamines sre operable. If desired, mixtures of dismlnes or mixtures of disulphonyl halides may be used to also facilitate precipitation or the insoluble salt of the polymeric sulphonamide. The" solvent usually is chosen from those solvents which do not reactwith the starting materials. Thus, di-

oxsn, toluene. xylene, nitrobonsens. or the others of ethylene :lycol referred to Is "Oellosolvc" British Patent No. 495,790)- ethers are examples of solvents that may be employed.

Since one molecule of hydrogen halide is liberated for each sulphonamide group'formed, and since the liberated hydrogen halide would immediately react with the diamine needed for further su'lphonation, it is necessary to provide for a suitable hydrogen halide acceptor. Convenient acceptors include excess diamine, aqueous sodium or potassium hydroxide, and potassium or. sodium carbonates; In place-oi excess diamine or caustic,

N,N-dimethylaniline, N,N-diethylaniline, pyridine or quinoiine can be used as acceptors. In addition tofunctioning as hydrogen halide acceptors, this, latter group of reagents also serve as diluents. When aqueous alkali is employed toaccept the hydrogen halide formed in the condensation, the

preferred temperature range is -10 C. to avoid I the possibility oi hydrolyzing the sulphonyl halide. It is also preferable to regulate the addition of the aqueous alkali so that it is not in excess over the hydrogen halide generated. Temperatures between 0 and 200 C. may be used when excess diamine is employed 'as the halogen halide ac- I c'eptor in an inert solvent. Under these conditionsQhowever, it is most convenient to add the disulphonyl halide to the diamine at a rate Just suflicient to keep the solvent refluxing.

Since the sulphonation is vigorous, the time for complete reaction is usually only one to two hours. Secondary diamines or branched chain disulphonyl halidesusually react more slowly, and com- I plete reaction in these cases may take as long as ten to twelve hours.

Usually, atmospheric pressure is employed because of convenience, although superandsubatmospheric pressures give equally good results. It is also desirable, although not essential, to carry out the reaction in an atmosphere free of acidic, basic or other reactive gases. Thus, the reaction may be carried out in an atmosphere free of carbon dioxide, sulphur dioxide, ammonia, or owgen.

It has been found that deoxidized nitrogen is suitable for blanketing the reaction mixture.

The extent of polymerization can be controlled by employing one of the ingredients in excess, or

by the use of certain mono-functional reactants which act as polymerization stabilizers (see Stabilizers include mono-primary or mono-secondary amines, such as aniline, butylamine, ethylamine, diethylamine,

and N-methyl aniline. Acidic stabilizers such as p-toluenesulphonyl halides, benzenesulphonyl halides, methanesulphonyl halides,- and butanesulphonyl halides also may be employed. These stabilizers usually are used in amounts varying from 0.5 to 2.0 mole per cent.

The new polymeric sulphonamides described I herein are particularly useful as emulsifying wherein R is a divalent aliphatic polymethylfinic widely different emhydrocarbon radical separating the two 80: groups by a chain containing at least three carbon atoms therein, R." is hydrogen, and R" is a .divalent aliphaltic polymethylenic hydrocarbon radical separating the amino groups by a chain containing at least two carbon atoms therein.

2. A polymeric sulphonamide free from carboxylic amide groups and having the recurring structural unit:

02SHO2-NR'R"NR' wherein R is a divalent aliphatic radical separating the two SO: groups by a chain containing at least three carbon atoms in 'said chain, each of said two $01 groups being directly connected to carbon in said chain, R is a member of the group consisting of hydrogen and monovalent hydrocarbon radicals. and R is a divalent organic,

radical separatingthe amino groups by a chain containing at least two carbon atoms in said chain, each of said two amino groups being-db rectly connected to carbon in said chain, R being.

connected to two and only two so: groups and R." being connected to two and only two amino groups as the sole groups reactive with sulphonyl halide and amino groups.

3. A process for the production of polymeric sulphonamides which comprises reacting together an' aliphatic disulphonyl halidev containing two .and only two sulphonyl halide groups as the sole reacting groups and a diamine containing two and only two amino groups as the sole reacting groups, the two sulphonyl groups of said aliphatic disulphonyl halide being separated by a chain containing at least three carbon atoms in said chain and being directly connected to carbon therein, the two amino groups of said diamine bee ing separated by a chain containing at least two carbon atomsin said chain and being directly connected to carbon therein, and each of the amino nitrogen atoms of said diamine being hydrogen-bearing and attached only to hydrogen and carbon atoms.

4. The process set forth in claim 9 in which the disulphonyl halide is para-cyclohexanedisulpho nyl chloride and the diamine is hexamethylenediamine.

5. The process set forth in claim 9 in which the disulphonyl halide is 1,3-propanedisulphonyl 'chlorideand the diamine is hexam ethylenediamine. v

6. A polymeric sulphonamide consisting of the recurring structural unit:

-O:SR.-SOzNR'-R' 'NR'- wherein'R is .an alkylene radical containing a chain length of at least three carbon atoms between the 802 groups, R," is a hydrocarbon radical having a chain length of at least two carbon atoms, and R is a member of the group consisting of hydrogen and monovalent hydrocarbon radicals.

'7. A process for-the production ofpolymeric sulphonamides consisting of the recurring structural unit:

which comprises reacting together, in the presence of a hydrogen halide acceptor, an allrylene disulphonyl halide of the formula XOzS-R-SOaX with a diamine of the formula HNW-RP-HNR; wherein X is a halogen, R is an alkylene radical having a-chain length of at least three carbon atoms between the 80: groups, R" is a hydrocarbon radical havlng a chain length of at least two carbon atoms..and B. is a member-of the group consisting 0! hydrogen and monovalent hydrocarbon radicals. H

8. A polymeric sulphonainide consisting of the recurring structural unit:

wherein R is an alkylene radicei containing a chain iength'of at least three carbon atoms between the 80: m ss, and R is a member oi the group consisting of erylene radicals, and oikylene radicals containing at Beast four carbon. et

l 9. A process for the production of polymeric sninhonam'ides consisting of the recurring stmc hire! unit:

which comprises reacting together; in the presence of a hydrogen halide acceptor an alkylene disuiphonyl halide of the formula XOaS-R-SOaX with a gliamine of the lormula HaN-R"N.H2;

9&2 1,890

wherein X is a halogen, R is an elkylene radical having a chain length of at least three carbon atoms between the SO: groups, and R" is a memher of the group consisting of erylene radicals. and alkvlene radicals containing at least four carbon atoms.

10. Poly-hexamethyiene-para. cyclohexsnedisulphonnmide.

11. Poly hexamethylene propanedisulphon amide.

12. The polymeric sulphonamide set forth in claim 3 where R" is a divalent aliphatic hydrocarbon radical.

13. The process which comprises reacting toaether in the presence or a hydrogen halide acceptor, th aliphatic disulphonyi halide and diemine set forth in claim 3.

14. The process whichcomprises reacting tonether in the presence oi a hydrogen halide accenter the aliphatic disulphonyl halide and; dinmine set forth in claim 3, where the disulphonyl halide is a. disulphonyl chloride. I

GWARD J. BERCHET. 

